Manufacture of new products comprising lignone derivatives



Patented Jan. 5, 1932 CHARLES FREDERIdK CROSS, OF LONDON, ENGLAND, AND ALF'ENGELSTAD, 0F VARDAL,

NORWAY.

MANUFACTURE on NEW rRonUcTscoMPnIsmG LIGNONE DERIVATIVES September 21, 1925.

This invention relates to the manufacture of new products comprising ligno-ne derivatives obtainable'as by-products in the manufacture of wood pulp from wood, andris a division of our United States application Serial No. 135,703, filed 15th September, 1926.

In the processes of pulping wood based on the action of aqueous sulphurous acid or bi sulphites, on the wood, the lignone components are obtained in a water-soluble form (conditioned by the acid group SO H in combination with the lignone complex) in the liquor; this liquor, after separation from the wood pulp, may be treated in various ways to yield products useful in-industry, for instance in tanning. The liquor may be concentrated, with or without such treatment, and with or without neutralization, until the content of solid material is comparatively high, without considerable loss of fluidity; for example the liquor may be con centrated until it contains over per cent.

of solid material, while still remaining more or less fluid. 4

In our aforesaid United States application Serial No. 135,703 (series of 1925) we have described the application of oxidation products made from the lignone derivatives obtainable by the sulphurous acid or bisulphite treatment of wood substance.

We have found that the water soluble condensation products which can be made from the lignone derivatives obtainable by the sulphurous acid or bisulphite treatment of wood substance (that is, the treatment of .wood' substance with aqueous sulphurous acid with or without the addition of a pro portion of a base such as lime or magnesia) have likewise a high solvent, and emulsifying or dispersing power in respect'of substances normally'immiscible with water, particularly hydrocarbons of high molecular weight. Thus, useful products can be made by mixing in any desired proportion the more concentrated solutions of condensation products of the I lignone derivatives, with hydrocarbons of high molecular weight, or with mixtures thereof, such as the tarsproduced in the destructive distillation of wood, coal or the like, or residues from the distilla- NO. 135,703, and in'Great Britain Divided and this application filed March 7, 1928. Serial No. 259,903.

tion of mineral oils, or natural products of a like character. The products may have the appearance of true solutions and may be diluted with water in moderate amounts without causing any appreciable separation; as the dilution is increased, a point is reached at which the product passes intothe form of a stable emulsion. The mixtures may also be mixed with many by-products of similar character, such as bitumen, cotton-seed pitch, and oils and fats, such as linseed-oil, tungoil, or tallow. Owing to the fact that the mixtures obtained by the invention may contain a considerable quantity of water, they may also be mixed with a number of soluble compounds, for instance with many dyestuffs, or with suitable inorganic salts, in order to modify the mixtures for particular applications.

When there are used, according to the invention, certain hydrocarbon mixtures of a less fluid nature, such as-bitumen, asphaltor the like, they are first brought into a fluid state by addition of a proportion of a suitable solvent, preferably a solvent hydrocarbon, before mixing with the solution of the lignone derivatives.

The condensation products of the lignone derivatives may be made by subjecting the latter, prior to admixture with the hydrocarbon or the like, to a preliminary treatment in relatively dilute solution with a substance adapted to cause condensation, such as hydrochloric acid or ferric chloride, after which the solution is evaporated until pasty, and the residue is taken up in water. The solution so obtained is, moreover, capable of dissolving substantial proportions of certain mineral oxides, such as hydrated ferric oxide.

The products obtainable in accordance with the invention find application for various purposes for which aqueous emulsions of hywaterv drocarbons are used, particularly as protective paints, and in the manufacture of weather-resistant 'fabrics such as roofing felt.

ly divided solids. In particular, the products obtained from the aforesaid lignone derivatives by condensation alone or with other substances, find a useful application in connection with solutions from which. undesirable insoluble deposits tend to separate, an addition of the aforesaid condensation products to such a solution preventing in many cases deposition of insoluble matter.

The invention is particularly applicable to the condensation products of the lignone derivatives obtained by the sulphurous acid treatment of wood described in U. S. Patent No. 1,547,907 of July 28, 1925 to C. Cross and British Patent No. 202,016.

The following examples illustrate the invention:

(1) The liquor from the sulphurous acid or bisulphite treatment of wood, is concen trated until the content of solid matter is about 37 per cent. To 100 parts byvolume of this concentrated extract are added 10 parts of concentrated hydrochloric acid, and

the mixture is evaporated on the water bath until it is in a pastycondition, approximating to dryness. The residue is taken up with water and the solution made up to the original volume of 100 parts by additions of' water and made up to the original volume of the concentrated lignone extract used as parent material, may be mixed readily with 10 parts of ferric oxide in the form of hydrate, which dissolves on warming the mixture. The product obtained by mixing this solution with tars (for example with 10 parts of coal tar or wood tar), as previously described, is useful for application to surfaces as a protectivepaint.

The exp'ress1on aqueous dispersions as used in the appended claims is intended to include any system in which the substance normally immiscible with water (for example, a hydrocarbon of high molecular weight) is dispersed throughout an aqueous medium, whet-her the substance is in solution in the medium, or emulsified or suspended therein.

The term treatment of wood with an.

aqueous solution containing sulphurous acid anions used in the appended claims is in tended to include the treatment of wood substance with aqueous sulphuio'us acid in ab- 1 woodwith an aqueous solution sence of a base, as well as. with aqueous sulphurous acid in presence of a. base such as lime or magnesia, or in presence oi? a small quantit of ammonia as described in said U. S. Patent llo. 1,547,907.

Having thus fully described the nature of the said invention and the best means We know of carrying the same into practical effect, we claim 2-- 1. A method of producing stable aqueous dispersions, of substances normally immiscible with water, which comprises forming a mixture containing water, a substance normally immiscible with water, and water-soluble condensation products of the soluble lignone derivatives obtainable by the treatment of wood with an aqueous solution containing sulphurous acid anions.

2. A process'for the manufacture of products comprising lignone derivatives, which process comprises incorporating a hydrocarbon of high molecular weight with a 'concentrated solution of water-soluble condensation products of the soluble lignone derivatives obtainable by the treatment of wood with an aqueous solution containing sulphurous acid anions.

3. A process for the manufacture of products comprising lignone derivatives, which process com rises treating a metal oxide and" a hydrocar on of high molecular wei ht with a concentrated solution of water-solu le condensation products of the soluble lignone derivatives obtainable by the treatment .of containing sulphurous acid anions.

4. 'A process for the manufacture of products comprising lignone derivatives, which process comprises treating hydrated ferric oxide and aihydrocarbon of high molecular weight with a concentrated solution of water-soluble condensation products of the soluble lignone derivatives obtainable by the treatment of wood with an aqueous solution containing sulphurous acid anions.

5. Aqueous dispersions comprising a solution of water soluble condensation products of the lignone derivatives obtainable by the treatment of wood with an aqueous solution containing sulphurous acid anions and a substance normally immiscible with water dispersed throughout said solution.

6. Aqueous dispersions comprising a solution of water soluble condensation products of the lignone derivatives obtainable by the treatment of woodwith an aqueous solution containing sulphurous acid anions'anda hydrocarbon of high molecular weight dispersed throughout said solution.

In testimony hereof we have'signed our names to'this specification.

CHARLES FREDERICKCROSS. [L. 8.]

ALF ENGELSTAD. v [L. s.] p 

